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Journal of Membrane Science 312 (2008) 614

Application of seawater to enhance SO2 removal from simulated

flue gas through hollow fiber membrane contactor
Xueyan Sun a,b , Fangang Meng a,c , Fenglin Yang a,
a School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116023, PR China
b School of Technology, China Agricultural University (Yantai), Yantai 264000, PR China
c Department of Chemical Engineering, Technische Universitat Berlin, Str. des 17. Juni 136, MA 5-7, 10623 Berlin, Germany

Received 6 March 2007; received in revised form 7 November 2007; accepted 4 December 2007
Available online 23 December 2007

Abstract
In this paper, seawater was applied as absorbent for the removal of sulfur dioxide (SO2 ) from flue gas in a hollow fiber membrane contactor. In
order to verify the application feasibility of seawater on SO2 removal, tap water, aqueous NaOH solution with a pH value of 8.35 and seawater
were used as absorbents, respectively. The impacts of various factors such as three different absorbents, pressure gradient between gas and liquid,
flow rate of absorbents, flow rate and concentration of feed gas on the overall mass transfer coefficient were investigated. The experimental results
indicated that owing to the existence of complex CO2 H2 OHCO3 CO3 2 equilibrium system, the mass transfer coefficient of seawater was
about twice as large as that of aqueous NaOH solution with pH value of 8.35. In addition, seawater could withstand the sudden increase of SO2
loading rate. When the pressure gradient between gas and liquid kept under the penetration pressure, the membrane contactor could obtain high
overall mass transfer coefficient, especially when seawater was used as absorbent. The height of transfer unit (HTU) of the membrane contactor
was relatively small, and HTU increased hardly with increasing flow rate of flue gas when seawater was used as absorbent. Membrane contactor
coupled with seawater absorption is a prospective technology for sulfur dioxide (SO2 ) removal in coastal area.
2008 Elsevier B.V. All rights reserved.

Keywords: Sulfur dioxide; Membrane contactor; Seawater; Flue gas desulfurization (FGD)

1. Introduction
Stricter legislations and environmental problems with acid
rain make it necessary to remove sulfur dioxide from flue gas.
An effective approach to control sulfur dioxide emissions is the
use of flue gas desulfurization (FGD) systems. Enormous efforts
have been made to develop new technologies which can not
only be installed conveniently but also be operated efficiently
and flexibly to meet special demands of various cases. As a
matter of fact, membrane contactor is an emerging and efficient
technology with many advantages over conventional contactors.
In conventional contactors, such as packed towers, spray tow-
ers, venture scrubbers or bubble columns, flue gas is usually
dispersed and contacted with liquid directly. There are many
drawbacks [1], such as foaming, emulsion, flooding or channel-
Corresponding author. Tel.: +86 411 84706172.
E-mail addresses: fgmeng80@126.com (F. Meng),
fenglinyang@126.com (F. Yang).
ing and bring huge space requirement, resulting in high capital
costs and loading limitations. Comparatively, membrane contac-
tors can realize gasliquid contacting operation through hollow
fiber membrane [2], in which the absorbent liquid flows on one
side and the gas flows on the other side of the membrane, such
fluid offers several advantages including high interfacial area
per unit volume, absence of emulsion, no flooding at high flow
rates and no unloading at low ones [3,4].
Because membrane contactor has so many desirable advan-
tages, many investigations have been carried out in the past
decades [515], and the effects of various factors on mass trans-
fer have been investigated, such as membrane structure [5],
membrane module [13], membrane wetting [7], enhancement
with chemical reactions [8,9] and activators [10]. Moreover, its
application for SO2 removal from flue gas has gained increasing
attentions recently [1113]. As a matter of fact, some pilot-scale
membrane contactors have been applied to recover CO2 or SO2
from the flue gas, which have been operated successfully for a
long time and obtained high absorption rate above 90% [14,15].
Recent years, the cost of membrane materials has reduced signif-

0376-7388/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2007.12.011
 X. Sun et al. / Journal of Membrane Science 312 (2008) 614 7

icantly, which lead membrane contactors to a wider application

in controlling acid gas emissions.
However, one of the factors that limit this technology so far for
SO2 removal is the capital cost of SO2 absorbent. In past works
[1113], the aqueous solutions of salts such as sodium hydroxide
(NaOH), sodium sulfate (Na2 SO4 ), sodium citrate, potassium
carbonate (K2 CO3 ), sodium sulfite (Na2 SO3 ), sodium hydro-
gen sulfite (NaHSO3 ) were tried as SO2 absorbents, which
have gained desirable absorption performance. But, the use of
these absorbents increased the capital cost of the flue gas desul-
furization (FGD) process and limited its practical industrial
application in areas where fresh water is not readily available.
Actually, seawater is a natural absorbent for SO2 removal,
which has an abundant resource in coastal areas and keep pH
level between 7.8 and 8.5 which due to the complex carbonate- Fig. 1. Schematic map of sampling location.
related system in it. Utilization of seawater to absorb SO2 in
power plant has become a promising and attractive method [16].
The earliest investigation of seawater for scrubbing SO2 from CaCO3  Ca2+ + CO3 2
stack gases was conducted at the University of California, Berke-
ley. The investigation showed the feasibility of using seawater to MgCO3  Mg2+ + CO3 2
absorb SO2 from stack gas [17]. Since then, series of seawater
FGD systems with scrubbers as contactors have been practi- NaCO3  Na+ + CO3 2
cally operated at many power plants in China, America, Europe
and Japan. Compared to the conventional wet limestone sys- KCO3  K+ + CO3 2
tems, the seawater FGD systems offer many advantages in terms
of process, design, operation and cost effectiveness [16]. How- CaHCO3 +  Ca2+ + HCO3
ever these systems cannot avoid the disadvantages caused by the
direct gasliquid contact in scrubber contactors. MgHCO3 +  Mg2+ + HCO3
To overcome the above-mentioned shortcomings in con-
ventional seawater FGD contactors, microporous hollow fiber NaHCO3  Na+ + HCO3
membrane contactor was used as SO2 absorber in this study and
the feasibility of seawater applied for absorbent to enhance SO2 KHCO3  K+ + HCO3
removal from simulated flue gas through membrane contactor
was investigated. This study aims at providing theoretical and The above-mentioned equilibriums indicate that seawater has
technical data for large scale SO2 removal by using membrane a large capacity for SO2 absorption, which can be obviously
contactor coupled with seawater absorption in the future. improved with the increase of HCO3 concentration. In this
study, the seawater was taken from the south coastal area of
2. Theory Dalian (shown in Fig. 1) and its physical characteristics are
presented in Table 1.
2.1. Components of seawater
2.2. Chemical process during seawater FGD
Natural seawater is a complex system, in which there is a
series of dissolved chemical components such as the constant As soon as the SO2 is dissolved into the seawater, the follow-
components and trace matters. The constant components include ing reactions are involved [20]:
Na+ , Mg2+ , Ca2+ , K+ , Sr2+ , Cl , SO4 2 , HCO3 and Br ,
SO2 (gas)  SO2 (liquid) (1)
which take up 99.899.9% of dissolved salt in seawater and
NaCl is about 85% of the constant component in seawater. The
Table 1
average pH value of natural seawater is about 7.88.5 and the Physical characteristics of seawater
alkalinity is approximately 1.22.5 mmol L1 , which is mainly
attributed to HCO3 [18]. The following equilibriums are the pH 8.208.35
Alkalinity (mmol/L) 1.942.22
carbonate-related system existing in natural seawater [19]: SO4 2 (mg/L) 3,051
HCO3 (mg/L) 149
H2 O + CO2  H2 CO3
Ca2+ (mg/L) 453
Na+ (mg/L) 13,067
H2 CO3  H+ + HCO3 Mg2+ (mg/L) 1,746
TSS (mg/L) 0.5
HCO3  H+ + CO3 2
COD (mg/L) 1.13
8 X. Sun et al. / Journal of Membrane Science 312 (2008) 614
SO2 (liquid) + H2 O  H2 SO3
H2 SO3  H+ + HSO3
HSO3  H+ + SO3 2
Generally, the above reactions can be described as the following
equilibriums:
SO2 + OH  HSO3
HSO3 + OH  SO3 2 + H2 O (6)
Then part of SO3 2 is oxidized to SO4 2 with the cataly-
sis of Cl and transition mental ions Fe2+ , Mn2+ and so on,
which is the key step for the Eqs. (5) and (6) to move right.
The detailed research about the mechanism of seawater FGD
has been reported by Zhao et al. [18].
2.3. Principle of membrane contactor for FGD
The principle of the hollow fiber membrane contactor for
FGD is illustrated in Fig. 2. The flue gas stream and the seawater
stream are separated by microporous hydrophobic membrane.
The SO2 passes into the liquid through the membrane pores,
where it is absorbed by the chemical components in the seawater.
As a matter of fact, the microporous membrane used in this pro-
cess acts as a fixed interface between the gas and the liquid phase
without dispersing one phase into another. The gasliquid inter-
face is immobilized in the pores of microporous membrane by
careful control of the pressure gradient between the two phases
under the penetration pressure.
The mass transfer process in the membrane contactor con-
sists of three steps in series: the transfer from gas phase to the
membrane surface, transfer within membrane pores and transfer
from liquid interface to the liquid bulk. The overall mass transfer
coefficient, K, can be described as follows [21,22]:
1 1 1 1
= + + (7)
K kg km Hkl
1 1 1 1
= + + (8)
K kg km Hkl
Fig. 2. Schematic illustration of SO2 removal by non-wetted hollow fiber mem-
brane.
(2) where kg , km and kl are individual mass transfer coefficients of
the gas phase, the membrane phase and the liquid phase, respec-
(3) tively. H is the physical solubility coefficient of the gaseous
species into the liquid bulk and is the enhancement factor in
(4)
mass transfer rate due to chemical reaction between SO2 and
seawater. The mass transfer coefficient of membrane phase, km ,
depends on the type of phase present in the membrane pores.
The mass transfer resistance of the gas filled (non-wetted) pores
(5) is usually very small and negligible. However, when the mem-
brane pores are filled with the liquid (wetted), the mass transfer
resistance of the membranes becomes significant [21,22]. So the
design strategy of the membrane gasliquid contactors for SO2
removal should be aimed at preventing the membrane wetting
for long-term application.
3. Experiment
3.1. Experimental setup
As polypropylene membrane has many favorable characteris-
tics such as non-polarity, high hydrophobic quality, low surface
tension and low surface energy, the microporous hydrophobic
polypropylene hollow fiber membrane was applied in the exper-
iment. The characteristics of the hollow fiber membrane are
listed in Table 2. Generally, parallel flow offers a high con-
centration gradient in the case of counter-current flow [23], so
the gas always flowed through the lumen side and the liquid
through the shell side of the membrane contactor conversely in
this experiment.
The experimental setup is shown in Fig. 3. The SO2 was intro-
duced into the system from compressed gas cylinders and the
air was provided by an air pump, which was dehydrated before
into the lumen side of membrane contactor. The simulated flue
gas was mixed with SO2 and dry air. Seawater from water pump
after simple filtration was employed as the absorbent. In addi-
tion, the tap water and NaOH solution with pH value of 8.35
were also used to absorb SO2 . The flow rate and pressure of gas
and liquid were adjusted by flow meters and inching switches,
which can regulate the gas flow rate. The fluid pressures were
indicated by the pressure gauges at the inlet and outlet. The inlet
and outlet gas streams were switched through a cross-valve to
Table 2
Characteristics of the membrane contactor used in this study
Module length (mm) 220
Membrane material Polypropylene
Membrane processing method Stretching
o.d. of fiber (m) 580620
i.d. of fiber (m) 480520
Thickness of membrane wall (m) 50
Fiber arrangement Parallel
i.d. of module (mm) 10
Number of fibers 64
Pore size (m) 0.070.1
Packing density (%) 2325
Theoretical contacting area (m2 ) 0.02654
Pressure gradient across membrane (kPa) 2.53.5
Flow mode Counter-current, parallel
 X. Sun et al. / Journal of Membrane Science 312 (2008) 614
Fig. 3. Schematic diagram of experimental apparatus.
the system of SO2 concentration analysis. The acidified seawa-
ter after reaction with SO2 in membrane contactor was aerated
by air pump and neutralized by natural seawater before being
discharged to the seawater body.
For each run of the experiment, sufficient gas pressure was
maintained in the contactor lumen side before starting the liq-
uid flow. The system was first operated for at least half an
hour to ensure that a steady state had been reached before data
collection. All the experiments were conducted at the room
temperature.
3.2. SO2 analytical system
The SO2 concentration of inlet and outlet gas streams was
determined by means of Sample-Fast lodometric method [24],
which had been used practically. It is proved that Sample-Fast
lodometric method is a fast, accurate and anti-jamming method
for SO2 concentration determination over General lodometric
method. Fig. 4 is the schematic diagram of this Sample-Fast
lodometric method.
Fig. 4. Schematic diagram of SO2 concentration determination.
9
This analytical method is based on the following chemical
reaction:
SO2 + I2 + H2 O H2 SO4 + 2HI (9)
The SO2 in gas mixture reacts with iodine in amylaceous
solution, and the residual gas is collected in the conical flask
and then, the volume of residual gas can be determined by the
scales on the tube for gas volume determination. The reaction of
Eq. (9) is complete when the last blue color of the amylaceous
solution vanishes, then the SO2 volume ratio can be calculated
according to the concentration of the iodine solution, volume of
the iodine solution, and residual gas on the basis of the following
equation:
MI2 VI2 21.89
= (10)
MI2 VI2 21.89 + V (273/(273 + t))
where MI2 is the concentration of iodine in amylaceous solution
(mol L1 ), VI2 is the volume of iodine solution (mL), V is the
volume of residual gas in conical flask (mL), t is the temperature
of residual gas ( C), is the SO2 volume ratio in gas mixture
(dimensionless).
The overall mass transfer coefficient can be calculated as
follows [25]:
Q g Ci
K= ln (11)
A C0
where K is the overall mass transfer coefficient (m s1 ), A is the
contacting area (m2 ), Qg is the flow rate of feed gas (L h1 ), Ci
is the SO2 volume ratio in feed gas (dimensionless), C0 is the
SO2 volume ratio in outlet gas (dimensionless).
In addition, the height of transfer unit (HTU), a measure of
the membrane module efficiency, is given by [26]:
Qg
HTU = (12)
KS
where HTU is the height of transfer unit (m), is the surface to
volume ratio of the membrane module (m2 m3 ), S is the cross-
section area of the membrane module (m2 ). The HTU is often
said to represent the efficiency of the membrane contactor: a
small HTU represents a high efficient separation [27]. From Eq.
(12) it can be seen that the HTU value is determined by flow rate
of feed gas and the overall mass transfer coefficient. The HTU
value will decrease with decreasing flow rate of feed gas or with
increasing overall mass transfer coefficient.
4. Results and discussion
4.1. Effect of absorbents ow rate on the overall mass
transfer coefcient
In Fig. 5, the results show that when absorbent flow rate was
not too high, the overall mass transfer coefficient increased sig-
nificantly as the absorbent flow rate increased. The boundary
layer between the solution and gas became thinner with increas-
ing the absorbent flow rate, which led to the increase of the
liquid phase mass transfer coefficient. In addition, the increase
of absorbent flow rate could carry away SO3 2 and HSO3 more
10 X. Sun et al. / Journal of Membrane Science 312 (2008) 614
Fig. 5. Effect of absorbents flow rate on SO2 overall mass transfer coefficient
Qg = 0.2 m3 h1 , Pg = 11 kPa, Pl = 9 kPa, = 1500 106 .
quickly and made the Eqs. (5) and (6) move right, which could
enhance the overall mass transfer coefficient too.
It also can be seen that the seawater had a higher overall mass
transfer coefficient than tap water and NaOH solution with pH
value of 8.35. With respect to tap water, the SO2 absorption
was mainly based on physical absorption. During the absorp-
tion process, the boundary layer was fully saturated by SO2 ,
additionally the SO3 2 and HSO3 could not be carried away
as soon as possible under low absorbent flow rate, which caused
the low SO2 absorption capability. With respect to NaOH solu-
tion, it had a higher SO2 absorption rate than tap water, which
is due to the chemical absorption by NaOH solution. During
the chemical absorption process, the reaction between SO2 and
NaOH could enhance the mass transfer coefficient, and acceler-
ate SO2 absorption process. From Fig. 5 it can be seen that when
the absorbents flow rate was larger than 60 L h1 , there was few
differences between NaOH solution and tap water, indicating
that the NaOH had few impacts on the enhancement of SO2
removal at high flow rate of NaOH solution. In addition, when
the flow rate of seawater was higher than 40 L h1 , the flow rate
of seawater had no influence on the overall mass transfer coeffi-
cient. These results suggest that under high absorbent flow rate
the mass transfer resistances of membrane and gas phase grad-
ually became the dominant factors for the overall mass transfer.
From Fig. 5 it can also be seen that the optimum flow rate of
seawater should be ranged in 3040 L h1 .
The absorption capability of seawater was much higher than
those of NaOH solution and tap water. This phenomenon could
be explained by the complex carbonate-related system in sea-
water. The SO2 absorption process in seawater was also mainly
based on chemical absorption. The mass transfer coefficient of
seawater was about twice as large as that of aqueous NaOH
solution with pH value of 8.35. It can be attributed to the
complex CO2 H2 OHCO3 CO3 2 equilibrium system in sea-
water, which provides the seawater with a higher capacity of
absorption. The following reactions occurred when SO2 was
absorbed in seawater besides Eqs. (1)(4):
H+ + CO3 2  HCO3
H+ + HCO3  CO2 + H2 O
From Eqs. (13) and (14) we can see that the complex
CO2 H2 OHCO3 CO3 2 equilibrium system in seawater
can compensate the decrease of alkalinity caused by FGD
process.
Thus, the seawater could maintain a lower mass transfer
resistance and correspondingly higher overall mass transfer
coefficient. When the flow rates of three absorbents were too
high, their SO2 absorption efficiency reached a limit value and
there were few differences among the mass transfer coefficients.
The coupled membrane contacting and chemical absorption
induced by alkalinity of seawater could enhance FGD process.
Yang and Cussler [28] observed a 10-fold increase in the gas
separation efficiency when using a hollow fiber device over a
conventional packed column. Ogundiran et al. [29] also reported
that hollow fiber membrane contactor was an extremely promis-
ing alternative to conventional scrubber used for FGD. Karoor
and Sirkar [2] reported as high as 99% SO2 removal efficiency in
a small membrane contractor using tap water. In their study, the
removal of SO2 was achieved by physical absorption, so it should
consume a great deal of water to absorb SO2 . A recent study by
Oikawa et al. [16] showed that seawater was a promising and
attractive alternative to conventional alkaline chemicals such as
limestone and magnesium hydroxide. They compared the sea-
water FGD and wet limestone FGD systems based on a large
power plant utilizing coal having 1% sulfur. They reported that
the seawater FGD could reach 9098% SO2 removal efficiency,
however, the wet limestone FGD obtained 8095% SO2 removal
efficiency. The previous reports, together with our data, indicate
that membrane contactor coupled with seawater absorption has
much better performances than conventional FGD systems using
packed column and alkaline chemicals.
4.2. Effect of pressure difference between gas and liquid on
the overall mass transfer coefcient
In this experiment, the pressures of gas phase and liquid phase
were controlled at 1020 kPa and 921 kPa, respectively. As
shown in Fig. 6, the SO2 absorption rate could maintain at a
high level when the P was controlled between 1.5 and 2.5 kPa
which equals to the gas phase pressure subtracted by the liq-
uid pressure. However, when the pressure gradient P between
two phases was too large, the overall mass transfer coefficient
would decrease correspondingly. It was because that when the
pressure difference between gas and liquid was kept under the
(13)
(14)
Fig. 6. Effect of pressure gradient between gas and liquid on SO2 overall mass
transfer coefficient. Qg = 0.1 m3 h1 , Ql = 30 L h1 , = 1500 106 .
 X. Sun et al. / Journal of Membrane Science 312 (2008) 614
penetration pressure, the two phases could realize a non-wetted
gasliquid contact mode as shown in Fig. 2 and the reaction
interface could be immobilized at the pore mouth of the micro-
porous membrane fiber in the liquid side, which could provide a
lower mass transfer resistance and a higher overall mass transfer
coefficient. In addition, the produced SO3 2 and HSO3 could
diffuse fast into the bulk liquid phase, resulting in a high overall
mass transfer coefficient.
When the pressure of liquid phase was too high, the liquid
would penetrate into the bulk gas phase and the pores were
filled with liquid, which decreased the mass transfer coefficient
of km in Eq. (8) and deteriorated the absorption of SO2 . On
the other hand, when pressure of gas phase was too high, the
gas penetrated into the bulk liquid phase, which disturbed the
gasliquid interface and brought air bubble to the bulk liquid
phase, resulting in the deterioration of SO2 absorption too.
Fig. 6 also shows that when seawater was used as an
absorbent, the overall mass transfer coefficient could keep at
a high level in a wider range of pressure difference compared
to tap water and aqueous NaOH solution. This can be explained
by YangLaplace equation as follows [26]:
2rcos c
Pcr =
rp
Here, the Pcr is the penetration pressure, r is the surface tension
of the absorbent, rp is the radius of the membrane pore and c is
the contact angle. From Eq. (15) it can be seen that when seawa-
ter is used as absorbent, the breakthrough pressure is higher than
that of tap water and aqueous NaOH solution, for seawater has
a larger surface tension. This also suggests that when seawater
was used as absorbent, the membrane module could withstand
a high-pressure difference between liquid phase and gas phase.
4.3. Effect of feed gas concentration on the overall mass
transfer coefcient
As presented in Fig. 7, when seawater flow rate was controlled
at a lower value, the overall mass transfer coefficient decreased
with the increase of feed gas concentration. For example, when
seawater flow rate was controlled at 8 L h1 , the overall mass
transfer coefficient decreased three times when the SO2 volume
ratio in the feed gas increased from 1500 to 2100 106 . How-
Fig. 7. Effect of feed gas concentration on SO2 overall mass transfer coefficient
when seawater as absorbent. Qg = 0.1 m3 h1 , Pg = 11 kPa, Pl = 9 kPa.
11
ever, when seawater flow was controlled at a higher flow rate
(30 L h1 ), the overall mass transfer coefficient was higher and
decreased slightly with the increase of feed gas concentration.
This result indicates that as the SO2 concentration was high,
a higher seawater flow rate could guarantee a high and steady
overall mass transfer.
When seawater flow rate was low, the absorption capacity
of seawater was relatively small and the produced SO3 2 and
HSO3 could not be carried away in time, even though there is
a carbonate-related system in seawater. Therefore, the low flow
rate of seawater resulted in high mass transfer resistance and
low absorption capability. That was the reason why under lower
seawater flow rate the overall mass transfer coefficient decreased
significantly with the increase of feed gas concentration. On the
other hand, when seawater was maintained at a high flow rate,
its absorption capacity increased and the produced SO3 2 and
HSO3 could be carried away as soon as possible, which results
in the increase of the enhancement factor, . Moreover, the mass
transfer resistance of liquid phase can be ignored under a high
seawater flow rate. Therefore, when seawater flows at a higher
rate, it can be concluded that the impact of feed gas concentration
on the overall mass transfer coefficient is very little.
(15)
4.4. Effect of gas ow rate on the overall mass transfer
coefcient
From Fig. 8 it can be seen that the overall mass transfer
coefficient increased as the gas flow rate increased from 0.1
to 0.2 m3 h1 . When the feed gas flow rate increased, there was
much SO2 molecule passing into membranes, and then the sea-
water had more chances to contact with SO2 molecule, leading
to the increase of the overall mass transfer coefficient. On the
other hand, when feed gas flow was at a rate above 0.3 m3 h1 ,
the overall mass transfer coefficient decreased as the feed gas
flow rate increased. This is because that when feed gas flow
rate was too high, the contact time between SO2 and absorbents
reduced and the absorption ability of seawater was limited, so
the overall mass transfer coefficient decreased regardless of the
decrease of mass transfer resistance in the gas phase boundary
layer. Thus, it can be concluded that the optimum gas flow rate
for seawater should be 0.3 m3 h1 , with given operating condi-
tions (Ql = 30 L h1 , = 1500 106 ). However, the optimum
Fig. 8. Effect of gas flow rate on SO2 overall mass transfer coefficient.
Ql = 30 L h1 , Pg = 11 kPa, Pl = 9 kPa, = 1500 106 .
12 X. Sun et al. / Journal of Membrane Science 312 (2008) 614
gas flow rates for tap water and NaOH solution were 0.2 m3 h1 .
These results further indicate that the seawater had a large capac-
ity on SO2 absorption.
From Fig. 8 it also can be seen that when the gas flow rate was
larger than 0.3 m3 h1 , compared to tap water the NaOH solution
had little impacts on the enhancement of overall mass transfer
coefficient; however, the overall mass transfer coefficient could
maintain a high value as seawater was used as absorbent. The
pH of the used NaOH solution was only 8.35, so the chemi-
cal absorption capability of NaOH solution was limited. From
these results it can be concluded that the seawater absorption
can obtain a sustainable operation under high or un-steady SO2
loading rate.
4.5. Outlet pH of membrane contactor
During the absorption, the pH value would change due to
the decrease of alkalinity. In this experiment, the outlet pH of
the membrane module was measured in order to understand the
absorption capability from the viewpoint of alkalinity consum-
ing. As shown in Fig. 9, the outlet pH value reached a steady
state after the system had been operated for half and an hour.
Under the operating conditions shown in Fig. 9, the pH value
of seawater decreased more gently with operating time as com-
pared with the tap water and aqueous NaOH solution. After
SO2 absorption, the pH values of tap water and NaOH solution
decreased to 6.86.9 and 7.07.1, respectively. Though seawater
has high capability on SO2 absorption, its pH value after absorp-
tion was the highest among the three absorbents, which reached
7.37.4 after absorption. This can be attributed to the bicarbon-
ate buffering system in seawater which made the seawater pH
value decrease more slightly during the absorption of SO2 .
During FGD process, the outlet pH value and the chem-
ical components of the absorbents would change due to the
presence of sulfite. When seawater is used as absorbent, the
seawater will discharge into sea again after FGD process. From
an environmental point of view, the changes of pH and chemical
components of seawater are of great concern, especially to the
local ecology [16]. Oikawa et al. [16] reported that blowing air
into the effluent could oxide sulfite to sulfate, which is less toxic.
And then, the pH of seawater would increase after blowing air. In
our study, the seawater, tap water and NaOH solution were aer-
Fig. 9. Evolution of effluent absorbent pH with time. Ql = 8 L h1 ,
Qg = 0.1 m3 h1 , Pg = 11 kPa, Pl = 9 kPa, = 1500 106 .
Fig. 10. Evolution of HTU value of membrane contactor with gas flow rate.
Ql = 30 L h1 , Pg = 11 kPa, Pl = 9 kPa, = 1500 106 .
ated after FGD process. The seawater pH value reached 7.87.9
after the following aeration. The pH values of tap water and
NaOH solution reached 7.37.4 and 7.47.5, respectively. After
being returned to the seawater body, the discharge pH increases
toward ambient values, depending on the mixing and diffusion
process.
4.6. Comparison of HTU
The HTU values of the membrane contactor were calculated
by using Eq. (12). The HTU data are shown in Fig. 10. It can
be seen that the HTU value of the membrane contactor was
smaller than 0.05 m when seawater was used as absorbent. But
the HUT values ranged from 0.04 to 0.25 m when tap water and
NaOH were used as absorbents. It suggests that the seawater had
higher absorption ability and smaller mass transfer resistance.
From Fig. 10, we can also notice that the HTU increased as flow
rate of feed gas increased, especially when tap water and NaOH
solution were used as absorbents. With respect to seawater, how-
ever, the increase of flow rate of feed gas had small impacts on
HTU. This result further indicates that seawater had large capa-
bility on SO2 absorption, and seawater could avoid the negative
impacts of high flow rate of feed gas on mass transfer.
It has been observed that the hollow fiber membrane in mem-
brane contactor can offer up to several times area than that of
conventional packed tower. From Table 3 it can be seen that
hollow fiber membrane had a much lower HTU than that of
conventional packed tower. The HTU is determined by operat-
ing conditions such as superficial velocity, gas concentration,
gas flow rate and so on. Obviously, the HTU is inversely pro-
portional to the surface to volume ratio, S. The large hollow
fiber area per volume or interface area was one of the reasons
Table 3
Comparison of HTU values of hollow fiber membrane and conventional packed
tower
HTU (m)
Packed tower [30] 0.61.8
Packed tower [31] 0.71.1
Hollow fiber membrane [2] 0.10.9
Hollow fiber membrane [27] 0.10.3
Our results 0.020.27
 X. Sun et al. / Journal of Membrane Science 312 (2008) 614
that lead to a low HTU. In addition, the flue gas can penetrate
membranes without any bubbles and contact with absorbents in
liquid phase, this is just like the bubbleless aeration in membrane
aerated biofilm reactor. Thus, the SO2 can be absorbed immedi-
ately as soon as it reaches the liquid. Lastly, as mentioned in the
section of introduction, the hollow fiber membrane can avoid
the direct gasliquid contact in scrubber contactors. That is why
the hollow fiber membrane contractor could obtain high mass
transfer efficiency or low mass transfer resistance. Therefore,
we can conclude that membrane contactor will be a promis-
ing and interesting technology for waste gas removal in the
future.
5. Conclusions
In this work, seawater was used as absorbent in hollow fiber
membrane contactor to remove sulfur dioxide from simulated
flue gas. From the experimental results, it can be concluded
that under the same operating conditions, seawater could keep
a high overall mass transfer coefficient which was about twice
as large as that of the aqueous NaOH solution with pH value of
8.35. Compared with the aqueous NaOH solution, the superior-
ity of seawater used as SO2 absorbent was especially significant
under the conditions of higher feed gas concentration and larger
feed gas flux, which indicate that seawater has a large capac-
ity on SO2 absorption. This phenomenon was mainly attributed
to the complex bicarbonate buffering system in seawater. After
SO2 absorption, the pH values of the absorbents decreased,
it is necessary to aerate the absorbents with air before being
discharged into seawater body. The seawater absorption cou-
pled with membrane contactor had a very lower HTU value
than conventional packed tower. Membrane contactor coupled
with seawater absorption is a prospective technology for sulfur
dioxide removal in seaside area.
Nomenclature
A contacting area (m2 )
C0 SO2 volume ratio in feed gas
Ci SO2 volume ratio in outlet gas
H physical solubility coefficient of the gaseous
species into the liquid bulk
kg mass transfer coefficient of gas phase (m s1 )
km mass transfer coefficient of membrane (m s1 )
kl mass transfer coefficient of liquid phase with
chemical reaction (m s1 )
kl mass transfer coefficient of liquid phase without
chemical reaction (m s1 )
K overall mass transfer coefficient (m s1 )
Pl pressure of feed absorbent (kPa)
P the pressure gradient between gas phase and liq-
uid phase (kPa)
Pcr breakthrough pressure between gas phase and liq-
uid phase (kPa)
Pg pressure of feed gas (kPa)
13
Qg flow rate of feed gas (L h1 )
Ql flow rate of feed liquid (m3 h1 )
r the surface tension of the absorbent
rp the radius of the membrane pore
S cross-section area of membrane module (m2 )
Greek symbols
surface to volume ratio of membrane module
(m2 m3 )
enhancement factor
c the contact angle
SO2 volume ratio in gas mixture
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